CN108550868B - Preparation method of nano metal oxide of anode of solid fuel cell - Google Patents
Preparation method of nano metal oxide of anode of solid fuel cell Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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Abstract
The invention discloses a preparation method of a special nano metal oxide for a solid fuel cell anode, belonging to the technical field of new energy battery materials. Firstly, mixing a cerium nitrate solution and a zinc nitrate solution, and adjusting the pH value to 6.0-6.4 to obtain an acidified mixed solution; mixing the acidified mixed solution and an ammonium silicate solution for reaction to obtain a colloidal dispersion liquid; adjusting the pH value of the obtained colloidal dispersion liquid to 11.4-11.6, and then carrying out hydrothermal reaction, filtering, washing and drying to obtain a dry filter cake; then calcining and activating the dried filter cake to obtain a calcined material; and heating, stirring and reacting the calcined material and a sodium hydroxide solution, filtering, washing and drying to obtain the special nano metal oxide for the anode of the solid fuel cell. The technical scheme of the invention can effectively avoid the agglomeration of the nano metal oxide in the preparation process, and the obtained product has narrow particle size distribution range, good dispersibility and high purity.
Description
Technical Field
The invention discloses a preparation method of a special nano metal oxide for a solid fuel cell anode, belonging to the technical field of new energy battery materials.
Background
In the modern society, with the rapid increase of economy, the global energy consumption is also rapidly increased. Research on high-efficiency, low-cost and environmentally-friendly renewable energy conversion and storage systems has become an increasingly popular research focus, and a fuel cell is an electrochemical device which directly converts chemical energy of gaseous or liquid fuel into electric energy through an oxidation-reduction reaction process, and does not undergo combustion, so that the fuel cell is not limited by carnot cycle and has high electrical conversion efficiency. In order to reduce excessive dependence on traditional fuels, ensure energy requirements and reduce environmental pollution, the extensive development of fuel cell technology will become the key point of research and development. The solid oxide fuel cell is a high-efficiency and environment-friendly power generation device. The high operating temperatures of conventional fuel cells promote reaction kinetics within the cell, thereby reducing the cell's need for noble metal catalysts. At such high temperatures, the hydrocarbon fuel can also be reformed within the cell to provide an excellent fuel gas for the fuel cell.
Due to the influence of the surface effect, the nano particles have large specific surface area, more surface active centers and good selectivity, and can obviously improve the catalytic efficiency. Nanoparticles have been internationally used as fourth generation catalysts, becoming the primary role of catalytic reactions. Cerium is a lanthanide and has good redox properties. Cerium oxide is an oxide catalyst with the highest activity in a rare earth oxide series, has a unique crystal structure, higher oxygen storage capacity, oxygen release capacity and stronger redox performance, is greatly concerned, has very important function in the electrochemistry of a fuel cell, and has the following advantages as a novel material, (1) the cerium oxide is a mixed conductor which can expand an anodic oxidation reaction surface to a TPB surface, (2) the cerium oxide has ionic conductivity larger than YSZ and can assist the electrolyte to transfer to an anode, (3): the cerium is easy to store and transmit oxygen, and the specific surface area of the nano-grade cerium is large, so that the oxygen storage capacity is improved.
The traditional nano metal oxide special for the anode of the solid fuel cell has low porosity and is easy to agglomerate, and certain difficulty is brought to practical application, so that the problem which needs to be solved urgently in the aspect of the nano metal oxide special for the anode of the solid fuel cell is also solved. Therefore, the research and development of the special nano metal oxide for the anode of the solid fuel cell, which has high porosity and is not easy to agglomerate, are very important.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the defects of low porosity and easy agglomeration of the special nano metal oxide for the anode of the traditional solid fuel cell, the preparation method of the special nano metal oxide for the anode of the solid fuel cell is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a special nano metal oxide for a solid fuel cell anode comprises the following specific preparation steps:
(1) mixing a cerium nitrate solution and a zinc nitrate solution, and adjusting the pH to 6.0-6.4 by using dilute nitric acid to obtain an acidified mixed solution;
(2) mixing the acidified mixed solution and an ammonium silicate solution for reaction to obtain a colloidal dispersion liquid;
(3) adjusting the pH value of the obtained colloidal dispersion liquid to 11.4-11.6, and then carrying out hydrothermal reaction, filtering, washing and drying to obtain a dry filter cake;
(4) calcining and activating the dried filter cake to obtain a calcined material;
(5) and heating, stirring and reacting the calcined material and a sodium hydroxide solution, filtering, washing and drying to obtain the special nano metal oxide for the anode of the solid fuel cell.
The mass fraction of the cerium nitrate solution in the step (1) is 10-12%.
The mass fraction of the zinc nitrate solution in the step (1) is 8-10%.
The volume ratio of the cerous nitrate solution to the zinc nitrate solution in the step (1) is 5: 1-10: 1.
and (3) the mass fraction of the ammonium silicate solution in the step (2) is 8-10%.
The volume ratio of the acidified mixed solution to the ammonium silicate solution in the step (2) is 3: 1-8: 1.
and (5) the mass ratio of the calcined material to the sodium hydroxide solution is 1: 3-1: 10.
and (5) the mass fraction of the sodium hydroxide solution is 10-20%.
The invention has the beneficial effects that:
the invention aims at providing a technical scheme which can effectively avoid cerium oxide from agglomerating in the preparation process, the influence of an auxiliary agent adopted in the preparation process on the final purity of a product is small, the prepared product has high porosity, firstly, the pH of a cerium nitrate solution and a zinc nitrate solution is adjusted to weak acidity, on one hand, the hydrolysis of the cerium nitrate and the zinc nitrate can be inhibited, on the other hand, in the mixing process of an acidic mixed solution and an ammonium silicate solution, hydrogen ions can be combined with silicate ions in a system to form orthosilicic acid, the orthosilicic acid is unstable and can be dehydrated mutually to form silicic acid colloid, the pH of the system slowly rises along with the consumption of the hydrogen ions, so that metal ions are hydrolyzed to gradually form hydroxide crystal nuclei, and once the hydroxide crystal nuclei are generated, the hydroxide crystal nuclei can be adsorbed and fixed by the silicic acid colloid, thereby effectively avoiding the further growth and agglomeration of hydroxide crystals, in the pH adjusting process of the step (3), the silicic acid colloid is re-dissolved to form a silicate solution, so that the template is removed, ammonium nitrate in the system is gradually decomposed in the hydrothermal reaction process, gas is generated, the gas generation process can effectively play roles of pore forming and further agglomeration prevention, so that a dry filter cake with a porous structure is formed, the dry filter cake is a mixture of porous cerium oxide and zinc oxide, the existence of the zinc oxide can play a role of steric hindrance, the agglomeration of the cerium oxide in the calcining process is effectively avoided, and in the final step (5), because the zinc oxide is an amphoteric metal oxide, the cerium oxide is insoluble in a strong base solution, the zinc oxide can be removed, the cerium oxide can be retained, the cerium oxide can be purified, the porosity can be further improved, and the high-purity nano cerium oxide with rich porosity can be finally prepared, the product is applied to the anode material of the solid fuel cell, and the cell performance can be effectively improved.
Detailed Description
And (2) mixing a cerium nitrate solution and a zinc nitrate solution according to a volume ratio of 5: 1-10: 1, mixing and pouring the materials into a No. 1 beaker, stirring and mixing the materials for 10 to 15min by using a glass rod, and then adjusting the pH value of the materials in the No. 1 beaker to 6.0 to 6.4 by using a dilute nitric acid solution with the mass fraction of 3 to 5 percent to obtain an acidified mixed solution; according to the volume ratio of 3: 1-8: 1, weighing an acidified mixed solution and an ammonium silicate solution, firstly pouring the ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel while stirring at a constant temperature under the conditions that the temperature is 55-65 ℃ and the rotating speed is 400-600 r/min, controlling the dropwise adding speed of the acidified mixed solution to be 2-5 mL/min, continuously stirring at the constant temperature for reacting for 2-4 h after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH value of materials in the hydrothermal kettle to 11.4-11.6 by using a sodium hydroxide solution with the mass fraction of 8-10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.4-0.6 MPa at the temperature of 185-200 ℃ and the rotating speed of 400-800 r/min, decompressing, filtering to obtain a filter cake, washing the filter cake with deionized water for 3-5 times, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 105-110 ℃ to obtain a dried filter cake; transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 480-500 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation, calcination and activation for 2-4 h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 10-20% according to the mass ratio of 1: 3-1: 10, pouring the mixture into a reaction kettle, stirring and reacting at a constant temperature of 55-60 ℃ at a rotating speed of 300-500 r/min for 4-8 h, filtering to obtain filter residue, washing the filter residue with deionized water until the washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying in vacuum until the weight is constant, and discharging to obtain the nano metal oxide special for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 10-12%. The mass fraction of the zinc nitrate solution is 8-10%. The mass fraction of the ammonium silicate solution is 8-10%.
Example 1
Mixing a cerium nitrate solution and a zinc nitrate solution according to a volume ratio of 10: 1, mixing and pouring the mixture into a No. 1 beaker, stirring and mixing the mixture for 15min by using a glass rod, and then adjusting the pH value of the material in the No. 1 beaker to 6.4 by using a dilute nitric acid solution with the mass fraction of 5 percent to obtain an acidified mixed solution; according to the volume ratio of 8: 1, pouring an ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature while dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel under the conditions that the temperature is 65 ℃ and the rotating speed is 600r/min, controlling the dropwise adding rate of the acidified mixed solution to be 5mL/min, continuously stirring at constant temperature for reacting for 4 hours after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.6MPa at the temperature of 200 ℃ and the rotating speed of 800r/min, decompressing and filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake; then transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 10, pouring the mixture into a reaction kettle, stirring the mixture at a constant temperature and a rotation speed of 500r/min for reaction for 8 hours, filtering the mixture to obtain filter residue, washing the filter residue with deionized water until a washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying the filter residue in vacuum until the weight of the washing liquid is constant, and discharging the product to obtain the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 12%. The mass fraction of the zinc nitrate solution is 10%. The mass fraction of the ammonium silicate solution is 10%.
Example 2
Pouring the cerium nitrate solution into a No. 1 beaker, stirring and mixing for 15min by using a glass rod, and then adjusting the pH value of the material in the No. 1 beaker to 6.4 by using a dilute nitric acid solution with the mass fraction of 5% to obtain an acidified mixed solution; according to the volume ratio of 8: 1, pouring an ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature while dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel under the conditions that the temperature is 65 ℃ and the rotating speed is 600r/min, controlling the dropwise adding rate of the acidified mixed solution to be 5mL/min, continuously stirring at constant temperature for reacting for 4 hours after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.6MPa at the temperature of 200 ℃ and the rotating speed of 800r/min, decompressing and filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake; then transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 10, pouring the mixture into a reaction kettle, stirring the mixture at a constant temperature and a rotation speed of 500r/min for reaction for 8 hours, filtering the mixture to obtain filter residue, washing the filter residue with deionized water until a washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying the filter residue in vacuum until the weight of the washing liquid is constant, and discharging the product to obtain the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 12%. The mass fraction of the ammonium silicate solution is 10%.
Example 3
Mixing a cerium chloride solution and a zinc chloride solution according to a volume ratio of 10: 1, mixing, pouring into a No. 1 beaker, stirring and mixing for 15min by using a glass rod, and adjusting the pH of the material in the No. 1 beaker to 6.4 by using a dilute hydrochloric acid solution with the mass fraction of 5% to obtain an acidified mixed solution; according to the volume ratio of 8: 1, pouring an ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature while dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel under the conditions that the temperature is 65 ℃ and the rotating speed is 600r/min, controlling the dropwise adding rate of the acidified mixed solution to be 5mL/min, continuously stirring at constant temperature for reacting for 4 hours after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.6MPa at the temperature of 200 ℃ and the rotating speed of 800r/min, decompressing and filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake; then transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 10, pouring the mixture into a reaction kettle, stirring the mixture at a constant temperature and a rotation speed of 500r/min for reaction for 8 hours, filtering the mixture to obtain filter residue, washing the filter residue with deionized water until a washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying the filter residue in vacuum until the weight of the washing liquid is constant, and discharging the product to obtain the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium chloride solution is 12%. The mass fraction of the zinc chloride solution is 10%. The mass fraction of the ammonium silicate solution is 10%.
Example 4
Mixing a cerium nitrate solution and a zinc nitrate solution according to a volume ratio of 10: 1, mixing and pouring into a No. 1 beaker to obtain a mixed solution; according to the volume ratio of 8: 1, pouring an ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature at 65 ℃ and at the rotating speed of 600r/min, dropwise adding the mixed solution into the three-neck flask through a dropping funnel while stirring at constant temperature, controlling the dropping rate of the mixed solution to be 5mL/min, continuously stirring at constant temperature for reacting for 4 hours after the dropwise adding of the mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.6MPa at the temperature of 200 ℃ and the rotating speed of 800r/min, decompressing and filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake; then transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 10, pouring the mixture into a reaction kettle, stirring the mixture at a constant temperature and a rotation speed of 500r/min for reaction for 8 hours, filtering the mixture to obtain filter residue, washing the filter residue with deionized water until a washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying the filter residue in vacuum until the weight of the washing liquid is constant, and discharging the product to obtain the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 12%. The mass fraction of the zinc nitrate solution is 10%. The mass fraction of the ammonium silicate solution is 10%.
Example 5
Mixing a cerium nitrate solution and a zinc nitrate solution according to a volume ratio of 10: 1, mixing and pouring the mixture into a No. 1 beaker, stirring and mixing the mixture for 15min by using a glass rod, and then adjusting the pH value of the material in the No. 1 beaker to 6.4 by using a dilute nitric acid solution with the mass fraction of 5 percent to obtain an acidified mixed solution; according to the volume ratio of 8: 1, pouring sodium silicate into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature and at the rotating speed of 600r/min while dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel, controlling the dropwise adding rate of the acidified mixed solution to be 5mL/min, continuously stirring at constant temperature for 4 hours after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloidal dispersion solution; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.6MPa at the temperature of 200 ℃ and the rotating speed of 800r/min, decompressing and filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake; then transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 10, pouring the mixture into a reaction kettle, stirring the mixture at a constant temperature and a rotation speed of 500r/min for reaction for 8 hours, filtering the mixture to obtain filter residue, washing the filter residue with deionized water until a washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying the filter residue in vacuum until the weight of the washing liquid is constant, and discharging the product to obtain the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 12%. The mass fraction of the zinc nitrate solution is 10%. The mass fraction of the sodium silicate is 10 percent.
Example 6
Mixing a cerium nitrate solution and a zinc nitrate solution according to a volume ratio of 10: 1, mixing and pouring the mixture into a No. 1 beaker, stirring and mixing the mixture for 15min by using a glass rod, and then adjusting the pH value of the material in the No. 1 beaker to 6.4 by using a dilute nitric acid solution with the mass fraction of 5 percent to obtain an acidified mixed solution; according to the volume ratio of 8: 1, pouring an ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature while dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel under the conditions that the temperature is 65 ℃ and the rotating speed is 600r/min, controlling the dropwise adding rate of the acidified mixed solution to be 5mL/min, continuously stirring at constant temperature for reacting for 4 hours after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into an oven, and drying at the temperature of 110 ℃ to constant weight to obtain a dried filter cake; then transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material; and mixing the obtained calcined material and a sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 10, pouring the mixture into a reaction kettle, stirring the mixture at a constant temperature and a rotation speed of 500r/min for reaction for 8 hours, filtering the mixture to obtain filter residue, washing the filter residue with deionized water until a washing liquid is neutral, transferring the washed filter residue into a vacuum drying oven, drying the filter residue in vacuum until the weight of the washing liquid is constant, and discharging the product to obtain the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 12%. The mass fraction of the zinc nitrate solution is 10%. The mass fraction of the ammonium silicate solution is 10%.
Example 7
Mixing a cerium nitrate solution and a zinc nitrate solution according to a volume ratio of 10: 1, mixing and pouring the mixture into a No. 1 beaker, stirring and mixing the mixture for 15min by using a glass rod, and then adjusting the pH value of the material in the No. 1 beaker to 6.4 by using a dilute nitric acid solution with the mass fraction of 5 percent to obtain an acidified mixed solution; according to the volume ratio of 8: 1, pouring an ammonium silicate solution into a three-neck flask, moving the three-neck flask into a digital display speed measurement constant-temperature magnetic stirrer, stirring at constant temperature while dropwise adding the acidified mixed solution into the three-neck flask through a dropping funnel under the conditions that the temperature is 65 ℃ and the rotating speed is 600r/min, controlling the dropwise adding rate of the acidified mixed solution to be 5mL/min, continuously stirring at constant temperature for reacting for 4 hours after the dropwise adding of the acidified mixed solution is finished, and discharging to obtain a colloid dispersion liquid; transferring the obtained colloidal dispersion liquid into a hydrothermal kettle, adjusting the pH of materials in the hydrothermal kettle to 11.6 by using a sodium hydroxide solution with the mass fraction of 10%, performing hydrothermal reaction until the pressure in the hydrothermal kettle reaches 0.6MPa at the temperature of 200 ℃ and the rotating speed of 800r/min, decompressing and filtering to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into a drying oven, and drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake; and transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material, namely the special nano metal oxide for the anode of the solid fuel cell. The mass fraction of the cerium nitrate solution is 12%. The mass fraction of the zinc nitrate solution is 10%. The mass fraction of the ammonium silicate solution is 10%.
Comparative example: the method is to mix the special nano metal oxide for the anode of the solid fuel cell produced by a certain nano technology development limited company.
The special nano metal oxide for the anode of the solid fuel cell and the comparative product obtained in the examples 1 to 7 are subjected to performance detection, and the specific detection method is as follows:
the porosity is measured by mercury porosimeter (Autopore 9500), the crystal structure and average particle size of the nanoparticles are measured by D/ma-rB type rotating anode target polycrystalline X-ray diffractometer, and the average particle size of the nanoparticles is calculated according to the crystallite dimension calculation formula of Sheer.
Specific detection results are shown in table 1:
TABLE 1 specific detection results of nano metal oxide for anode of solid fuel cell
The detection results in table 1 show that the nano metal oxide special for the anode of the solid fuel cell prepared by the technical scheme of the invention has the characteristics of excellent porosity, narrow particle size distribution range, good dispersibility and high purity, and has wide prospects in the development of the new energy battery material technology industry.
Claims (8)
1. A preparation method of a solid fuel cell anode nano metal oxide is characterized by comprising the following specific preparation steps:
(1) mixing a cerium nitrate solution and a zinc nitrate solution, and adjusting the pH to 6.0-6.4 by using dilute nitric acid to obtain an acidified mixed solution;
(2) mixing the acidified mixed solution and an ammonium silicate solution for reaction to obtain a colloidal dispersion liquid;
(3) adjusting the pH value of the obtained colloidal dispersion liquid to 11.4-11.6, and then carrying out hydrothermal reaction, filtering, washing and drying to obtain a dry filter cake;
(4) transferring the obtained dry filter cake into a muffle furnace, carrying out temperature programming to 480-500 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation, calcination and activation for 2-4 h, cooling to room temperature along with the furnace, and discharging to obtain a calcined material;
(5) and heating, stirring and reacting the calcined material and a sodium hydroxide solution, filtering, washing and drying to obtain the special nano metal oxide for the anode of the solid fuel cell.
2. The method for preparing the nano metal oxide for the anode of the solid fuel cell according to claim 1, wherein the mass fraction of the cerium nitrate solution in the step (1) is 10-12%.
3. The method for preparing nano metal oxide for the anode of the solid fuel cell according to claim 1, wherein the mass fraction of the zinc nitrate solution in the step (1) is 8-10%.
4. The method for preparing nano metal oxide for anode of solid fuel cell according to claim 1, wherein the volume ratio of cerium nitrate solution to zinc nitrate solution in step (1) is 5: 1-10: 1.
5. the method for preparing nano metal oxide for anode of solid fuel cell as claimed in claim 1, wherein the mass fraction of the ammonium silicate solution in step (2) is 8-10%.
6. The method for preparing nano metal oxide of anode of solid fuel cell as claimed in claim 1, wherein the volume ratio of the acidified mixed solution and the ammonium silicate solution in step (2) is 3: 1-8: 1.
7. the method for preparing nano metal oxide of anode of solid fuel cell according to claim 1, wherein the mass ratio of the calcined material and the sodium hydroxide solution in step (5) is 1: 3-1: 10.
8. the method for preparing nano metal oxide for anode of solid fuel cell according to claim 1, wherein the mass fraction of the sodium hydroxide solution in the step (5) is 10-20%.
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| CN101920984A (en) * | 2010-08-11 | 2010-12-22 | 中国科学院合肥物质科学研究院 | Method for preparing mesoporous CeO2 nano-tubes having large specific surface area and high catalytic activity |
| CN107488366A (en) * | 2016-06-13 | 2017-12-19 | 航天特种材料及工艺技术研究所 | A kind of method of silicon dioxide modified phyllosilicate powder |
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| CN101920984A (en) * | 2010-08-11 | 2010-12-22 | 中国科学院合肥物质科学研究院 | Method for preparing mesoporous CeO2 nano-tubes having large specific surface area and high catalytic activity |
| CN107488366A (en) * | 2016-06-13 | 2017-12-19 | 航天特种材料及工艺技术研究所 | A kind of method of silicon dioxide modified phyllosilicate powder |
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